Search Images Maps Play YouTube News Gmail Drive More »
Sign in
Screen reader users: click this link for accessible mode. Accessible mode has the same essential features but works better with your reader.

Patents

  1. Advanced Patent Search
Publication numberUS2950952 A
Publication typeGrant
Publication dateAug 30, 1960
Filing dateMay 8, 1958
Priority dateMay 8, 1958
Also published asCA934130A, CA934130A1, DE1098930B, DE1806154A1
Publication numberUS 2950952 A, US 2950952A, US-A-2950952, US2950952 A, US2950952A
InventorsNancy A Acara, Donald W Breck
Original AssigneeUnion Carbide Corp
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Crystalline zeolite t
US 2950952 A
Abstract  available in
Images(6)
Previous page
Next page
Claims  available in
Description  (OCR text may contain errors)

(IRYSTALLINE ZEOLITE T Donald W. Brock, Tonawanda, and Nancy A. Acara, Kenmore, N.Y., assignors to Union Carbide Corporation, a corporation of New York No Drawing. Filed May 8, 1958, Ser. No. 733,819

11 Claims. (Cl. 23-113) This invention relates to a novel composition of matter, and to a process for preparing and utilizing this novel material. More particularly, the invention is concerned with a novel synthetic member of the zeolite family.

The term zeolite, in general, refers to a group of naturally occurring hydrated metal aluminosilicates, many of which are crystalline in structure. The synthetic material of the invention bears a structural similarity to certain of the natural crystalline zeolites. Accordingly, the term synthetic crystalline zeolite is applied to the materials prepared by the process of the invention. There are, however, significant differences between the synthetic and natural materials. For convenience and distinguishability, the synthetic crystalline material of the invention will be referred to hereinafter as zeolite T.

Crystalline zeolites structurally consist basically of an open three-dimensional framework of SiO, tetrahedra. The tetrahedra are cross-linked by the sharing of oxygen atoms, so that the ratio of oxygen atoms to the total of the aluminum and silicon atoms is equal to two, or O/(Al-l-Si) =2. The negative electrovalence of tetrahedra containing aluminum is balanced by the inclusion Within the crystal of cations, e.g., alkali metal ions such as sodium and potassium ions.

The crystal structure of many zeolites also exhibit interstices of molecular dimensions. The interstitial spaces are generally occupied by water of hydration. Under proper conditions, viz., after at least partial dehydration, these zeolites may be utilized as efiicient adsorbents whereby adsorbate molecules are retained within the interstitial spaces. Access to these channels is had by way of orifices in the crystal lattice. The openings limits the size and shape of the molecules that can be adsorbed. A separation of mixtures of foreign molecules based upon molecular dimensions, wherein certain molecules are adsorbed by the zeolite while others are refused, is therefore possible. It is this characteristic property of many crystalline zeolites that has led to their designation as molecular sieves. in addition to molecular size and shape, however, other factors may also influence the selective adsorption of certain foreign molecules by molecular sieves. Among these factors are: the polarizability and polarity of the adsorbate molecules; the degree of unsaturation of organic adsorbates; the size and polarizing power of the interstitial cation; the presence of adsorbate molecules in the interstitial spaces; and the degree of hydration of the zeolite.

A number of synthetic crystalline zeolites have been prepared. They are distinguishable from each other and from the naturally occurring material on the basis of their composition, crystal structure and adsorption properties. A suitable method for distinguishing these compounds, for example, is by their X-ray powder diffraction patterns. The existence of a number of zeolites having similar but distinguishable properties advantageously permits the se- Patented Aug. as, seen lection of a particular member having optimum properties for a particular use.

The present invention has as its prime object of the wherein x is any value from about 0.1 to about 0.8, and y is any value from about 0 to about 8. Minor variations in the mole ratios of these oxides within the ranges indicated by the above formula do not significantly change the crystal structure or physical properties of the zeolite.

In addition to composition, zeolite T can be identified and distinguished from other zeolites and other crystalline substances by its X-ray powder diffraction pattern, the data for which are set forth below in Table A. In obtaining the X-ray powder diffraction pattern, standard techniques were employed. The radiation was the K- alpha doublet of copper, and a Geiger counter spectrometer with a-strip chart pen recorder was used. The peak heights 1, and the positions as a function of 26, Where 6 is the Bragg angle, were read from the spectrometer chart. From these, the relative intensities 1001/1 where i is the intensity of the strongest line or peak, and d(A.) observed, the interplanar spacing in Angstrom units corresponding to the recorded lines, were determined. in Table A, the more significant interplanar spacings, i.e., d (A.) values, for zeolite T are given; the relative intensities of the lines are expressed as VS (very strong), S (strong), M (medium) and W (weak).

Thus, zeolite T can be defined as a synthetic crystalline aluminosilicate having an X-ray powder diffraction pattern characterized by at least those interplanar spacing values set forth in Table A. The X-ray data given in Table B is for a typical example of zeolite T.

The X-ray powder dilfraction pattern for zeolite T indicates orthorhombic unit cells having repeat distances of 6.62 Angstrom units in one cell dimension, 11.5 Angstrom units in a second cell dimension and 15.1 Angstrom units in the third cell dimension.

The particular X-ray technique and/or apparatus employed, the humidity, the temperature, the orientation of the powder crystals and other variables, all of which are Well known and understood to those skilled in the art of X-ray crystallography or dilfraction, may cause some variation in the intensities and positions of the X-ray lines. Thus, the X-ray data given herein to identify zeolite T are not to exclude those materials which, due to some variable mentioned above or otherwise known to those skilled in the art, fail to show all of the tabulated X-ray lines, or show a few extra ones permissible to the Table B An 1 Iillierllgtelatige Bra e 20 p nnar ens y gg g Spacing, 100/1 crystal system of the zeolite, or show a slight change in intensity or shift in position of some of the X-ray lines as set forth in Table A.

Zeolite T can also be distinguished by the size and habit of its crystals. Prepared as hereinafter described, the zeolite is formed as a fine white crystalline powder. Electron micrographs of the powder indicate its external crystalline form to be generally rod-shaped. As a typical .example of crystal size, crystals of the zeolite were found by electron micrographs to measure firom about 3 to about 4 microns in length and from about 0.5 to about 0.6 microns in width.

In an embodiment of the present invention, zeolite T is prepared by suitably heating an aqueous sodium-potassium aluminosilicate mixture whose composition, expressed in terms of mole ratios of oxides, preferably falls within the following ranges:

Na O/(Na O+K O) of from about 0.7 to about 0.8 (Na O+K O)/SiO of from about 0.4 to about 0.5 SiO /Al O of from about 20 to. about 28 H o/(Na O-l-K O) of from about 40 to about 42 The desired product is thereby crystallized out relatively free from zeolites of dissimilar crystal structure. Zeolite T can also be prepared along with other zeolitic compounds by employing a reaction mixture whose composition, expressed in terms of mole ratios of oxides, falls within the following ranges:

Na O/(Na O+K O) of from about 0.7 to about 0.8 (Na O-|K O)/SiO- of from about 0.34 to about 0.44 SiO /Al O of from about 15 to about 30 H O/ (Na O-t-K O) of from about to about 51 In making zeolite T, the usual method comprises dissolving sodium aluminate or alumina trihydrate, and alkali, viz., sodium and potassium hydroxide, in water, and adding this solution to a water solution of sodium silicate, or preferably to a water-silicate mixture derived at least in part from an aqueous colloidal silica solution. The resultant mixture is placed in a suitable container made, for example, of metal or glass. The container should be closed to prevent loss of water. The reaction mixture is then stirred to insure homogeneity.

The crystallization procedure can satisfactorily be carried out at temperatures within the range of from about C. to about 150 C., the pressure being atmospheric, or at least that corresponding to the vapor pressure of water in equilibrium with the mixture of reactants. Preferably a temperature of approximately 100 C. is employed. Any convenient heating apparatus, e.g., an oven, sand bath, oil bath, or jacketed autoclave, can be used. Heating is continued until the desired crystalline zeolite product is formed. The zeolite crystals are then filtered off and washed to separate them from the reactant mother liquor. The zeolite crystals should be washed, preferably with distilled water, until the effluent wash water in equilibrium with the product has a pH of be tween about 9 and 12. As the zeolite crystals are washed, some of the sodium and potassium ions in the zeolite may be removed and are believed to be replaced by hydrogen ions. If the washing is discontinued when the pH of the effluent wash water is about 10, the

molar ratios of the crystalline product will be between about 0.9 and 1.0. Excessive washing will result in a somewhat lower value for this ratio, while insufiicient washing may leave slight excesses of sodium and potassium associated with the product. Thereafter, the zeolite crystals may be dried, conveniently in a vented oven.

Typicalof the manner in which zeolite T can be pre pared are the following examples.

EXAMPLE 1 A solution containing 30 grams of sodium aluminate, 73.2 grams of sodium hydroxide, and 41.1 grams of potassium hydroxide in 507 grams of water was added to 745 .2 grams of an aqueous colloidal silica solution containing 29.5 percent SiO by weight. The resulting mixture, having a composition, expressed in terms of mole ratios of oxides, as follows:

X-ray analysis of the product indicated a powder diffraction pattern characteristic of zeolite T, as set forth above in Tables A and B.

EXAMPLE 2 A solution containing 5.0 grams of alumina trihydrate, 15.3 grams of sodium hydroxide, and 7.16 grams of potassium hydroxide in 86.1 grams of water was added to grams of an aqueous colloidal silica solution containing 29.5 percent SiO by weight. The resulting mixture, having a composition, expressed in terms of mole ratios of oxides, as follows:

was then stirred until homogeneous. 'Crystallization of the desired zeolite product was carried out by heating the reactant mixture in a sealed glass jar at a temperature of 100 C. for approximately 88 hours. The crystalline product which formed had thereupon settled in the jar, and the reactant mother liquor Was clear. The crystalline product was then filtered, washed vwth water until the eflluent wash water had a pH of about 10.5 and dried. X-ray analysis of the product indicated a powder diffraction pattern characteristic of zeolite T, as set forth above in Table A.

EXAMPLE 3 A solution containing 5.0 grams of sodium aluminate, 15.9 grams of sodium hydroxide, and 8.57 grams of potassium hydroxide in 127.3 grams of water was added to 124.2 grams of an aqueous colloidal silica solution containing 29.5 percent SiO by weight. The resulting mixture, having a composition, expressed in terms of mole ratios of oxides, as follows:

Na O/(Na O-l-K O) Of 0.74 Of 0.5 SiO /A1 O Of 28 H O/ (Na20+K20) 0f 40 was then stirred until homogeneous. Crystallization of the desired zeolite product was carried out by heating the reactant mixture in a sealed vessel at a temperature of 120 C. for approximately 8 hours. The crystalline product which formed had thereupon settled in the vessel, and the reactant mother liquor was clear. The crystalline product was then filtered, washed with water until the efiluent wash had a pH of about 10.5, and dried. X-ray analysis of the product indicated a powder difiraction pattern characteristic of zeolite T, as set forth above in Table A.

EXAMPLE 4 In a manner similar to that described in Example 1 an aqueous sodium-potassium aluminosilicate mixture was prepared, having a composition, expressed in terms of mole ratios of oxides, as follows:

Na O/ (Na O+K O) of 0.74 (Na O-I-K O) /SiO of 0.38 SiO A1 0 of 28 I-I O/ (Na O-i-K o) of 42 This mixture was stirred until homogeneous. Crystallization of the desired product was carried out by heating this reactant mixture in a sealed 3-liter pressure vessel at a temperature of 150 C. for approximately 22 hours. The crystalline product which formed had thereupon settled in the vessel, and the reactant mother liquor was clear. The crystalline product was then filtered, washed with Water until the effluent wash water had a pH of about 10.5, and dried. X-ray analysis of the product indicated a diifraction pattern characteristic of zeolite T, as set forth above in Table A.

For satisfactory use as an adsorbent, zeolite T should be activated by at least partial dehydration. Such activation can be performed, for example, by heating the zeolite to temperatures of approximately 300 C. under atmospheric or reduced pressure, or by maintaining the zeolite at room temperature under vacuum.

Unlike common adsorbents, such as charcoal and silica gel, which show adsorption selectivities based primarily on the boiling point or critical temperature of the adsorbate, zeolite T exhibits a selectivity based on the size, degree of unsaturation, shape, polarity and polarizability of the adsorbate molecule. Among those adsorbate molecules whose size and shape are such as to permit adsorption by the zeolite, a strong preference is exhibited toward those that are polar, polarizable, unsaturated and straight-chained. This selectivity renders the zeolite most useful in the separation of polar from less polar or nonpolar molecules; polarizable from less polarizable or nonpolarizable molecules; unsaturated hydrocarbon molecules from corresponding less unsaturated or saturated molecules; and straight-chained aliphatic hydrocarbon molecules from branch-chained aliphatic, cyoloaliphatic and aromatic hydrocarbon molecules.

It is to be noted that the rejection characteristics of zeolite T are as important as the adsorption characteristics. The interstitial channels of the zeolite are such that at their narrowest points, molecules with critical dimensions greater than approximately 5.0 Angstrom units will not readily enter into the channels. The term critical dimension as employed herein may be defined as the maximum dimension of the minimum projected cross-section of the adsorbate molecule. The term may also be defined as the diameter of the smallest cylinder which will accommodate a model of the adsorbate molecule using the best available values of bond distances, bond angles and' Van der Waals radii. Hence, molecules having critical dimensions greater than approximately 5 .0 Angstrom units will be rejected by the zeolite, while those having smaller critical dimensions will be adsorbed.

Another property of zeolite T which contributes to its usefulness is that of adsorbing relatively large quantities of adsorbate at either very low pressures or concentrations. The novel material of this invention can therefore be utilized as a selective adsorbent in numerous gas or liquid separation processes, whereby small molecules such as water are separated from mixtures with other materials. The zeolite may also find use in cyclic adsorption-desorption processes for water and other adsorbates.

Samples of zeolite T, prepared from an aqueous sodiumpotassium aluminosilicate solution as described above, and which had been activated by dehydration at a temperature of approximately 300 C. under vaccum, were tested to determine their adsorption properties. The results obtained are set forth in Table C. The adsorption properties were measured in a McBain adsorptive system. The zeolite samples were placed in light aluminum buckets suspended from quartz springs. They were activated in situ, and the gas or vapor under test was then admitted to the system. The gain in weight of the adsorbent was measured by the spring extensions as read by a cathetometer. In Table B, the pressure given for each adsorption is the pressure of the adsorbate. The term Weight Percent Adsorbed refers to the percentage increase in the weight of the adsorbent.

The tabulated adsorption data show that water is more strongly adsorbed than any other material at comparable temperatures and pressures and illustrates a major use of zeolite T, i.e., the removal of water from mixtures containing water. An example of the use to be made of the property of strong adsorption at low pressures is the dr ing of a stream of air or other gases that contains only small amounts of water initially. For instance, with air containing water at a temperature of 25 C. and a partial pressure of 0.1 millimeters of mercury, zeolite T adsorbs approximately 7.5 percent by weight of water. Under similar conditions, silica gel adsorbs only about 1 percent by weight of water. Similarly, this property of strong adsorption at low pressures may be utilized in the recovery of traces of ethylene, acetylene, propylene, bute ne and other gases from by product or waste gas streams, or in the operation of adsorption processes at higher temperatures than are normally used with common adsorbents.

under similar conditions of temperature and pressure for straight-chained aliphatic hydrocarbons such as propane as compared with the corresponding cycloaliphaic hydrocarbons such as cyclopropane and with branched-chain aliphatic hydrocarbons such as iso-butane.

Zeolite T can be used as an adsorbent for the purposes indicated above in any suitable form. For example, a column of powdered crystalline material may give excellent results as may a pelleted form obtained by pressing into pellets a mixture of the zeolite and a suitable bonding agent such as clay..

What is claimed is:

1. A synthetic crystalline zeolite having a composition, expressed in terms of mole ratios of oxides, as follows:

tern essentially the same as that shown in Table A Table C Table A Pressure, Weight; Interplanar Spacing Relative Iuterplanar Spacing Relative Adsorbate Temp, 0. mm. Hg Percent d(A.) Intensity d(A.) Intensity Adsorbed p 0 vs 3.58;!;0.05 M 0.1 7.5 W W 11,0 25 4.5 16.2 M M 20 18.2 M s 0.1 8.4 W w 0: 196 13.5 3.72:1:005 3 23810.05 w

100 15.8 m 0.1 so Argon 196 10 2 i3 1 2. A synthetic crystalline zeolite according to claim 1, Pmpane 25 %gg wherein "y is about zero.

10 1 3. A synthetic crystalline zeolite having a composition, PmPYlene 25 gg expressed in terms of mole ratios of oxides, as follows:

10 6.6 ll-Penmne 25 88 0.49Na O:0.7lK O:Al O :6.6SiO :6.3H O

10 011 Oyelopropane 25 too 0.3 said synthetlc crystalline zeohte having an X-ray powder 1503mm; 25 tgg 2 diffraction pattern essentially the same as that shown in Th op n $8 2.3 Table A: Benzene 5O Table A 1 ,0 Interplanar Spacing Relative Interplanar Spacing Relative 10 3.2 25 d(A.) Intensity d(A.) Intensity 25 100 7.3

700 10.0 10 1.7 113:1:02 VS 3.58:|=0.05 M Butane-1 25 100 2. 7 7.45:0.15 W w 700 3.3 6.6=l=0.10 M M 1 2,4 4335:005.-- M 3 NH: 25 100 6,6 3.83=1=0.05 W w 700 7. s 3.72:3:005. s w

1 17.0 Krypton 1s3 10 23.1

18 23.5 V Cydohemne 25 68 4. A process for preparing a crystalline zeolite having a composition, expressed in terms of mole ratios of oxides, as follows: The greater affinity of zeohte T for adsorbate molecules possessing a greater degree of p y. polarlzablhty d 1.1 -0.4[xNa 0:(1-x)K 0] :A1 o :6.9:0.5sio 11 o unsaturation can also be seen from the tabulated adsorption data. For example, the data illustrate the adsorptive wherein x is any value from about 0.1 to about 0.8, and selectivity of the zeolite Tunder similar conditions of temy is any value from about 0 to about 8, said crystalline perature and pressure for unsaturated aliphatic compounds zeolite having an X-ray powder diffraction pattern essensuch as propylene and butene as compared with the corretially the same as that shown in Table A sponding saturated compounds propane and butane, and for unsaturated aromatic hydrocarbons such as benzene, bl A as compared with corresponding saturated cyclic hydrocarbons such as cyclohexane. The data also indicate that mterplanar Spacing Behave Inter-planar Spacing Relative orgamc sulfur compounds, generaly more polar or polardtA.) ns ty M Intensity izable than their hydrocarbon counterparts, are more strongly adsorbed by zeolite T than are their hydrocarbon g s 3.58:1:a05 M counterparts. For instance, under similar conditions of M W temperature and pressure the zeolite T evidences a greater selectivity for thiophene than for benzene. The data fur- 3:72 0:05 s ther serve to demonstrate the greater aflinity of zeolite T Na O/ (Na O+K O) of from about 0.7 to about 0.8 (Na O-Q-K O) /SiO of from about 0.4 to about 0.5 SiO /Al O of from about 20 to about 28 H O/ (Na o-i-KgO) of from about 40 to about 42 and maintaining such mixture at a temperature of between about C. and about C. until the desired crystalline zeolite product is formed.

5. A process for preparing a crystalline zeolite having a composition, expressed in terms of mole ratios of oxides,

wherein x is any value from about 0.1 to about 0.8, and

y is any value from about 0 to about 8, said crystalline aesdese zeolite having an X-ray powder difiraction pattern essentially the same as that shown in Table A zeolite having an X-ray powder diffraction pattern essentially the same as that shown in Table A Table A Table A 5 Interplanar Spacing Relative Interplanar Spacing Relative Interplanar Spacing Relative Interplanar Spacing Relative d (A Intensity d (A.) Intensity d (A.) Intensity d (A Intensity VS 325810.05 M VS 3 58510.05 M W .05 W W 33053.05 W M M M 3 =|=0.05 M M S M 2.85;|;0.05 S

W W 267310.05 W S W S 2.48i0.05 W

which process comprises preparing an aqueous sodiumpotassium aluminosilicate mixture whose composition, expressed in terms of mole ratios of oxides, falls within the following ranges:

Na O/ (Na O+K O) of from about 0.7 to about 0.8 (Na O-|-K O) /SiO of from about 0.34 to about 0.44 SiO /Al O of from about 15 to about 30 H O/ (Na O+K O) of from about to about 51 and maintaining such mixture at a temperature of between about 100 C. and about 150 C. until the desired crystalline zeolite product is formed.

6. A process for preparing a crystalline zeolite having a composition, expressed in terms of mole ratios of oxides, as follows:

1.1 [xNa O:

wherein x is any value from about 0.1 to about 0.8, and y is any value from about 0 to about 8 said crystalline zeolite having an X-ray powder difiraction pattern essentially the same as that shown in Table A Table A Interplanar Spacing Relative Interplanar Spacing Relative d(A.) Intensity MA.) Intensity which process comprises preparing an aqueous sodiumpotassium aluminosilicate mixture whose composition, expressed in terms of mole ratios of oxides, falls within the following ranges:

Na O/ (Na O+K O) of from about 0.7 to about 0.8 (Na O-I-K O) /SiO of from about 0.4 to about 0.5 SiO A1 0 of from about 20 to about 2'8 H O/ (Na O+K O) of from about 40 to about 42 maintaining such mixture at a temperature of approximately 100 C. until the desired crystalline zeolite product is formed, and separating the resultant crystals from the reactant mother liquor.

7. Process according to claim 6 including the additional step of washing said separated resultant crystals with water until the efiluent wash water in equilibrium with said crystals has a pH value of between about 9 and 12.

8. A process for preparing a crystalline zeolite having a composition, expressed in terms of mole ratios of oxides, as follows:

wherein x is any value from about 0.1 to about 0.8, and

y is any value from about 0 to about 8 said crystalline which process comprises preparing an aqueous sodiumpotassium aluminosilicate mixture whose'composition, expressed in terms of mole ratios of oxides, falls within the following ranges:

Na O/ (Na O|-K O) of from about 0.7 to about 0.8 (Na O+K O) /Si0 of from about 0.34 to about 0.44 SiO /Al O of from about 15 to about 30 H O/'(Na O+K O) of from about 20 to about 51 said crystalline zeolite having an X-ray powder diffraction pattern essentially the same as that shown in Table A Table A Interplanar Spacing Relative Interplanar Spacing Relative d (A.) Intensity d (A Intensity VS M W W M M M S W W S W which process comprises forming an aqueous sodiumpotassium aluminosilicate mixture whose composition, expressed in terms of mole ratios of oxides is maintaining such mixture at a temperature of about C. until crystals are formed having the desired composition, and separating the crystals from the reactant mother liquor.

11. A process for preparing a crystalline zeolite having a composition, expressed in terms of mole ratios of oxides, as follows:

wherein x is any value from about 0.1 to about 0.8, and

y is any value from about 0 to about 8, said crystalline zeolite having an X-ray powder diffraction pattern essentially the same as that shown in Table A Table A Interplanar Spacing Relative Interplanar Spacing Relative MA.) Intensity MA.) Intensity VS M W M M M S W W S W which process comprises preparing an aqueous sodiumpotassium aluminosilicate mixture whose composition, expressed in terms of mole ratios of oxides, falls within the following ranges:

N21 (Na O+:K O) of from about 0.7 to about 0.8 (Na o +K O) /SiO of from about 0.4 to about 0.5 SiO A1 0 of from about 20 to about 238 H O/ (Na O+K O) of from about 40 to about 42 References Cited in the file of this patent UNITED STATES PATENTS Barrer Dec. 29, 1942 Barret Dec. 24, 1946 Richmond et a1. Dec. 31, 1957 Christensen et al Dec. 31, 1957 Ballard et a1 Dec. 31, 1957 Sensel July 1, 1958 Estes Aug. 12, 1958 OTHER REFERENCES Barter et al.: J. Chem. Soc. 1952, pages 1561-1571. Barrer: J. Soc. Chem. Ind. (London), 1945, pp.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2306610 *Jan 31, 1942Dec 29, 1942Maling Barrer RichardFractionation of mixtures of hydrocarbons
US2413134 *Aug 22, 1944Dec 24, 1946Maling Barrer RichardProcess for the manufacture of crystalline absorbents
US2818137 *Oct 24, 1955Dec 31, 1957Texas CoAdsorptive separation process
US2818449 *Apr 8, 1955Dec 31, 1957Texas CoMethod for separation of organic mixtures
US2818455 *Mar 28, 1955Dec 31, 1957Texas CoDesorption of straight chain hydrocarbons from selective adsorbents
US2841471 *Oct 23, 1956Jul 1, 1958Texas CoSynthesis of selective mineral sorbents
US2847280 *Oct 23, 1956Aug 12, 1958Texas CoProduction of selective mineral sorbents
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3078644 *Jan 19, 1960Feb 26, 1963Union Carbide CorpMethod for adsorbing and separating unsaturated aliphatic hydrocarbons
US3130006 *Dec 30, 1959Apr 21, 1964Union Carbide CorpDecationized molecular sieve compositions
US3216789 *Aug 3, 1962Nov 9, 1965Union Carbide CorpCrystalline zeolite l
US3306922 *Mar 22, 1961Feb 28, 1967Union Carbide CorpMolecular sieve adsorbents
US3316691 *May 31, 1966May 2, 1967Union Carbide CorpFluid encapsulation product
US3375205 *Nov 13, 1962Mar 26, 1968Mobil Oil CorpSynthetic zeolite
US3405632 *Sep 3, 1965Oct 15, 1968Beloit CorpCalender loading mechanism
US3474025 *Apr 28, 1967Oct 21, 1969Mobil Oil CorpShape selective hydrocarbon conversion over activated offretite
US3625880 *Oct 15, 1969Dec 7, 1971Exxon Research Engineering CoCatalysts for the selective conversion of straight-chain hydrocarbons
US3640680 *Oct 28, 1968Feb 8, 1972Mobil Oil CorpMethod of decreasing the potassium content of potassium-containing zeolites
US3720753 *Feb 22, 1971Mar 13, 1973Exxon Research Engineering CoMethod for preparing a small pore synthetic zeolite
US3925191 *Jul 17, 1974Dec 9, 1975Mobil Oil CorpHydrocarbon conversion over activated erionite
US3950496 *Mar 27, 1975Apr 13, 1976Mobil Oil CorporationSynthetic zeolite ZSM-18
US4086186 *Nov 4, 1976Apr 25, 1978Mobil Oil CorporationCrystalline zeolite ZSM-34 and method of preparing the same
US4093699 *Nov 10, 1976Jun 6, 1978Zeochem CorporationSynthetic zeolite
US4116813 *Nov 16, 1977Sep 26, 1978Mobil Oil CorporationHydrocarbon conversion with crystalline zeolite ZSM-34
US4452958 *May 23, 1983Jun 5, 1984Mobil Oil CorporationOlefin polymerization with catalysts derived from chromium exchanged zeolites
US4522800 *May 5, 1983Jun 11, 1985Hoechst AktiengesellschaftProcess for the production of a crystalline aluminosilicate zeolite
US4554146 *Nov 10, 1983Nov 19, 1985Exxon Research And Engineering Co.Process for preparing a zeolite of the L type using organic templates
US4687653 *Nov 7, 1985Aug 18, 1987Toyo Soda Manufacturing Co., Ltd.Process for preparation of zeolite OE having an offretite type structure
US4804802 *Jan 25, 1988Feb 14, 1989Shell Oil CompanyIsomerization process with recycle of mono-methyl-branched paraffins and normal paraffins
US4931266 *Oct 22, 1986Jun 5, 1990Union Oil Company Of CaliforniaCrystalline galliosilicate with the erionite-type structure
US4946579 *May 1, 1989Aug 7, 1990Union Oil Company Of CaliforniaChemical conversion processes utilizing catalyst containing crystalline galliosilicate molecular sieves having the erionite-type structure
US5064793 *May 1, 1989Nov 12, 1991Union Oil Company Of CaliforniaCatalyst composition containing a crystalline galliosilicate having the erionite-type structure
US5118483 *Sep 27, 1991Jun 2, 1992The British Petroleum Company P.L.C.Crystalline (metallo) silicates and germanates-suz-4
US5385718 *Jun 18, 1991Jan 31, 1995Imperial Chemical Industries PlcZeolites
US5446234 *Oct 5, 1993Aug 29, 1995Imperial Chemical Industries PlcHydrocarbon conversion process using a specified zeolite
US5464799 *Nov 9, 1994Nov 7, 1995Imperial Chemical Industries PlcZeolite NU-85 catalyst
US5714133 *Oct 25, 1995Feb 3, 1998Mobil Oil CorporationCrystalline aluminosilicate zeolite syntheses
US6159542 *Jul 26, 1999Dec 12, 2000Mitsui Engineering & Shipbuilding Co., Ltd.Process for producing a membrane for separating a mixture
US6174941Jun 18, 1999Jan 16, 2001Witco Vinyl Additives GmbhNH2-modified 6-aminouracils as stabilizers for halogenated polymers
US6211270Jun 2, 1999Apr 3, 2001Witco Vinyl Additives GmbhCyanoacetylureas for stabilizing halogenated polymers
US6274654Jun 22, 1999Aug 14, 2001Witco Vinyl Additives Gmbh1,3-Disubstituted 6-aminouracils for stabilizing halogenated polymers
US6387269 *Jul 26, 1999May 14, 2002Bayer AktiengesellschaftMembrane for separating fluids
US6752980Mar 21, 2003Jun 22, 2004Uop LlcUZM-16: a crystalline aluminosilicate zeolitic material
US7344694Oct 6, 2004Mar 18, 2008Uop LlcUZM-12 and UZM-12HS: crystalline aluminosilicate zeolitic compositions and processes for preparing and using the compositions
US8198352May 14, 2009Jun 12, 2012Arkema FranceHigh purity monoalkyltin compounds and uses thereof
US8221717Aug 25, 2009Jul 17, 2012Florida State University Research FoundationFormulation and method for improved ion exchange in zeolites and related aluminosilicates using polymer solutions
US8987162Feb 24, 2012Mar 24, 2015Ut-Battelle, LlcHydrothermally stable, low-temperature NOx reduction NH3-SCR catalyst
US9196902Jul 4, 2011Nov 24, 2015Max-Planck-Gesellschaft Zur Foerderung Der Wissenschaften E. V.Phosphate- and silicate-based electrode materials, more particularly for lithium ion batteries and lithium capacitors
US9289756Jul 15, 2011Mar 22, 2016Basf SeCopper containing ZSM-34, OFF and/or ERI zeolitic material for selective reduction of NOx
US9409786Jul 3, 2014Aug 9, 2016Chevron U.S.A. Inc.Molecular sieve SSZ-98
US9416017Jul 3, 2014Aug 16, 2016Chevron U.S.A. Inc.Method for making molecular sieve SSZ-98
US9475039Mar 19, 2015Oct 25, 2016Ut-Battelle, LlcHydrothermally stable, low-temperature NOx reduction NH3-SCR catalyst
US9694352Sep 28, 2016Jul 4, 2017Ut-Battelle, LlcMethod for treating engine exhaust by use of hydrothermally stable, low-temperature NOx reduction NH3-SCR catalysts
US9700878Jul 2, 2015Jul 11, 2017Chevron U.S.A. Inc.Processes using molecular sieve SSZ-98
US20040242739 *Jun 21, 2002Dec 2, 2004Peter DauteUse of fluoroalkane sulfonic acids for stabilising organic plastics containing halogen
US20060189731 *Jul 8, 2004Aug 24, 2006Stephane GiroisStabilizing composition for chlorine-containing polymers
US20080153174 *Dec 20, 2006Jun 26, 2008Galloway Douglas BCatalytic alloy hydrogen sensor apparatus and process
US20080154432 *Dec 20, 2006Jun 26, 2008Galloway Douglas BCatalytic alloy hydrogen sensor apparatus and process
US20080154433 *Dec 20, 2006Jun 26, 2008Galloway Douglas BCatalytic Alloy Hydrogen Sensor Apparatus and Process
US20080154434 *Dec 20, 2006Jun 26, 2008Galloway Douglas BCatalytic Alloy Hydrogen Sensor Apparatus and Process
US20100047161 *Aug 25, 2009Feb 25, 2010Florida State University Research FoundationFormulation and method for improved ion exchange in zeolites and related aluminosilicates using polymer solutions
US20110166268 *May 14, 2009Jul 7, 2011Arkema FranceHigh purity monoalkyltin compounds and uses thereof
CN101014536BApr 20, 2004May 11, 2011环球油品公司Uzm-16: a crystalline aluminosilicate zeolitic material
DE102010026613A1Jul 9, 2010Jan 12, 2012MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V.Neue Phosphat- und Silikat-basierte Elektrodenmaterialien, insbesondere für Lithiumionen-Batterien und Lithiumkondensatoren
EP0073482A2 *Aug 26, 1982Mar 9, 1983Hoechst AktiengesellschaftBoron-containing aluminium silicates having a zeolitic structure, process for producing the same and their use
EP0073482A3 *Aug 26, 1982Oct 26, 1983Hoechst AktiengesellschaftBoron-containing aluminium silicates having a zeolitic structure, process for producing the same and their use
EP0074651A1 *Sep 11, 1982Mar 23, 1983Hoechst AktiengesellschaftZeolites containing gallium and/or indium, process for producing them and their use
EP0094023A1 *May 4, 1983Nov 16, 1983Hoechst AktiengesellschaftZeolites containing zirconium and/or hafnium, process for producing them and their use
EP0094024A1 *May 4, 1983Nov 16, 1983Hoechst AktiengesellschaftZeolites containing titanium, process for producing them and their use
EP0094025A1 *May 4, 1983Nov 16, 1983Hoechst AktiengesellschaftCrystalline aluminosilicate zeolites, process for producing them and their use
EP0106643A2 *Oct 7, 1983Apr 25, 1984Tosoh CorporationNovel zeolite and process for preparation thereof
EP0106643A3 *Oct 7, 1983Sep 12, 1984Toyo Soda Manufacturing Co., Ltd.Novel zeolite and process for preparation thereof
EP0111147A1 *Nov 2, 1983Jun 20, 1984Hoechst AktiengesellschaftZeolites containing titanium, zirconium and/or hafnium, process for producing them and their use
EP0785020A1Dec 11, 1996Jul 23, 1997L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges ClaudeProcess for separating mixtures of oxygen and nitrogen using an adsorbent with improved porosity
EP2123659A1May 15, 2008Nov 25, 2009Arkema FranceHigh purity monoalkyltin compounds and uses thereof
EP2593212B1Jul 13, 2011Dec 16, 2015Basf SeCopper containing zsm-34, off and/or eri zeolitic material for selective reduction of nox
WO2005113438A1 *Apr 20, 2004Dec 1, 2005Uop LlcUzm-16: a crystalline aluminosilicate zeolitic material
WO2012003954A2Jul 4, 2011Jan 12, 2012Max-Planck-Gesellschaft zur Förderung der Wissenschaften e. V.New phosphate- and silicate-based electrode materials, more particularly for lithium ion batteries and lithium capacitors
WO2013120792A1Feb 11, 2013Aug 22, 2013Basf SePvc compositions of high impact strength
WO2014122075A1Jan 31, 2014Aug 14, 2014Basf SeLubricant compositions for thermoplastic polymers
WO2016003502A1Mar 24, 2015Jan 7, 2016Chevron U.S.A. Inc.Molecular sieve ssz-98
WO2016003503A1Mar 24, 2015Jan 7, 2016Chevron U.S.A. Inc.Method for making molecular sieve ssz-98
WO2016003504A1Mar 24, 2015Jan 7, 2016Chevron U.S.A. Inc.Processes using molecular sieve ssz-98
WO2017068415A1Oct 21, 2016Apr 27, 2017Chemson Polymer-Additive AgVinyl chloride polymers and compositions for additive manufacturing
Classifications
U.S. Classification423/718, 502/77, 208/2, 423/332, 502/60
International ClassificationC01B39/30, C01B33/40, B01J20/18, B01J29/00, C01B39/00, C01B39/04, B01J29/50
Cooperative ClassificationB01J29/50, C01B39/30, C01B39/305
European ClassificationB01J29/50, C01B39/30, C01B39/30B